CN102329404B - Composite modified graft starch for textile slurry and preparation method thereof - Google Patents
Composite modified graft starch for textile slurry and preparation method thereof Download PDFInfo
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- CN102329404B CN102329404B CN 201110233283 CN201110233283A CN102329404B CN 102329404 B CN102329404 B CN 102329404B CN 201110233283 CN201110233283 CN 201110233283 CN 201110233283 A CN201110233283 A CN 201110233283A CN 102329404 B CN102329404 B CN 102329404B
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Abstract
The invention discloses a proportioning and preparing method for producing graft starch and particularly relates to composite modified graft starch for textile slurry. The composite modified graft starch for the textile slurry comprises the following raw materials in parts by weight according to proportion: 900 parts of acetate starch, 80-100 parts of alcohol, 40 parts of acrylamide, 10 parts of acrylic acid, 40 parts of vinyl acetate, 5 parts of caustic soda flakes, and 0.2-0.5 part of composite catalyst; and the requirements on the viscosity of the acetate starch is that L (Low Viscosity) is 4.0-0.0mPa.S, M (Middle Viscosity) is 8.1-12.0mPa.S, H (High Viscosity) is 12.1-16.0mPa.S, and the degree of substitution is 0.10+/-10%. According to the invention, a small amount of alcohol is adopted for production for the first time in China, and two problems to be solved on no utilization of water resources and no wastewater emission and treatment are solved. Ternary mixed monomers are grafted onto starch macromolecules under the condition of the alcohol solvent. Therefore, the serous coat performance of starch slurry is greatly improved, the requirements of textile manufactures on the starching of high-count polyester/cotton varieties, and the composite modified graft starch can replace PVA (Polyvinyl Acetate) to perform environment-friendly starching.
Description
Technical field
The present invention is a kind of proportioning and preparation method who produces graft starch, specifically relates to a kind of producting proportion and preparation method who is used for the complex denaturation graft starch that spinning sizing agent uses.
Background technology
Graft starch is used very wide in fields such as additive for papermaking and petroleum industry and textile sizings, warp sizing is the important manufacturing procedure together that weaving is produced, and directly influences loom efficiency and quality product.Used slurry mainly contains starch, PVA and acrylic size three major types in the warp sizing." few with or without PVA " become one of slurry development trend.Grafting modified starch is considered to one of suitable slurry that substitutes PVA.Many slurries factory with use factory and all relatively pay close attention to the certain situation relevant with grafting modified starch.
The starching of polyester-cotton fabric generally all adopt Z 150PH (PVA) be main chemosynthesis slurry as the main body tackiness agent, but be that main slurry slurries are difficult for hotting plate with PVA, skinning and form slime spots easily, dried leasing difficulty is bleachinged and dyeing the destarch trouble, and causes environmental pollution.Since the eighties in last century; Various modified starches have obtained fast development, and the first-generation sex change graft starch that utilizes ative starch to make through chemical degradation is wherein arranged, and graft starch is to be key with starch; Connect the product of skill copolymerization by the monomer that possesses sizing performance; Be the main slurry of textile warp starching from now on, gordian techniquies such as starch pre-treatment, initiator and monomer selection, graft process carried out experimental study, according to these processing condition; Can be made into graft starch excellent property, the plant produced normal use, obvious economic benefit and good social effect are arranged.
For a long time, grafting modified starch sizing agent is difficult to be used to effectively wash/Copolymer Grafting In Sizing Fine, and a major cause is that hydrophobic acrylic ester monomer is difficult for being grafted on the starch polymer chain.To cause the best cerium salt of effect is initiator, causes hydrophilic monomer and on starch, during grafting, can reach higher value, and percentage of grafting surpasses 100% sometimes.But high cerium ion causes hydrophobic monomer on starch during grafting, and much then little, percentage of grafting generally is difficult to surpass 40%.Though percentage of grafting is higher sometimes, grafting efficiency and monomer conversion are lower, and this is to have no alternative but sacrifice grafting efficiency or monomer conversion in order to improve percentage of grafting.Cause the best high cerium ion of effect at present when initiating methacrylates class monomer, even it is like this to cause effect, non-high cerium ion initiator effect is poorer.The costing an arm and a leg of high cerium ion, output are limited, and this has restricted the development of grafting modified starch sizing agent undoubtedly.The bad percentage of grafting that causes of the initiation performance of non-high cerium ion initiator is on the low side, causes the sizing performance of grafting modified starch sizing agent limited.
The research of grafting modified starch sizing agent and application still are in the desk study stage; Research mainly concentrates on whether gelatinization of starch, the kind of starch, the kind of initiator, monomeric kind and some reaction parameters; The degree of depth of research is not enough with systematicness, and most studies only limits in the laboratory.In the production effect preferably grafting modified starch sizing agent seldom, most needs of just selling propaganda, the effect of excessively exaggerative its product.
Though grafting modified starch sizing agent is a kind of premium quality product, not all grafting modified starch sizing agent performance necessarily is superior to other starch; Percentage of grafting is not to be the bigger the better yet, and has a best percentage of grafting; Though the dry production modified starch has certain advantage, the not modified starch of suitable for producing better performances, the more not high performance grafting modified starch of suitable for producing.
Since in the starch graft copolymer reaction at present suitable initiator seldom, the basic research of starch-grafted sex change and the shortcoming of applied research; Cause the progress of grafting modified starch sizing agent slow; The current necessary starch-grafted sex change Study on Technology of strengthening makes grafting modified starch sizing agent be applied to sizing production early.
The teacher of Xi'an University of Engineering Science & Technology is appealing that China's slurry industry is faced with domestic and international slurry manufacturer and cut-throat competition, and particularly internationally famous in recent years braiding slurry brand is landed successively and set up factories in China; Make on the spot, and China produces many, the small scale of number of the enterprise of modified starch, equipment is outmoded; Backward in technique, the scientific research insufficient investment, new product development lags behind; Go down for a long time, the kind of slurry, performance certainly will be eliminated as not catching up with requirement high-grade on the assembling-disassembling.
Traditional graft starch all is in water condition wet production, and shortcoming is that the technological process of production is long, needs to produce a large amount of trade effluents with a large amount of water logging bubble, washing, environment is posed a big pressure very not environmental protection of production process.
Summary of the invention
Plan of the present invention provides a kind of method of wet production graft starch under the water condition at present that is different from; Reach that to overcome in the wet production technological process of production long; Need to produce a large amount of trade effluents, environment is made the big defective of pressure with a large amount of water logging bubble, washing.
The objective of the invention is to realize through following technical scheme:
The complex denaturation graft starch that a kind of spinning sizing agent is used, proportioning are the raw material of following weight part:
900 parts of acetate starchs
Volumetric concentration 95～98% alcohol 80-100 parts
40 parts of acrylic amides
10 parts in vinylformic acid
40 parts of vinyl acetate between to for plastics
5 parts in sheet alkali
Composite catalyst 0.2-0.5 part;
The finished product: 996 weight parts ± 5%
The viscosity of said acetate starch requires:
L：4.0-8.0mPa.S
M：8.1-12.0mPa.S
H：12.1-16.0mPa.S
Substitution value: 0.10 ± 10%.
Alcohol consumption 80-100 part mainly is to consider cost and technological problems.The alcohol consumption is big more, helps reacting homogeneity, and to changing the benefit that is dispersed with of article in the reaction system, reaction efficiency also can improve.But the stirring resistance in the reactor drum can increase very big.In the actually operating, stir resistivity, can read from the current data of motor.With the 900kg acetate starch is example, behind the alcohol consumption of arrival 100kg, and every increase 20kg alcohol, current of electric increases 5A.So take all factors into consideration the condition of cost and processing unit, confirm that the alcohol consumption is 80-100 part.
The viscosity of raw material acetate starch is the actual needs of considering the user of textile mills.Some client needs the higher kind of viscosity, and some client needs the low kind of viscosity, should have the kind of different viscosity scope as supplier, satisfies the market requirement of differentiation.Various data be reinforced before, just measured and to have learnt.
Further, said composite catalyst is composited by cerous sulfate and Potassium Persulphate.
The making method of the complex denaturation graft starch that a kind of spinning sizing agent is used, step comprises:
In the box reactor drum of band strong mixer, add acetate starch, be heated to 40-50 ℃ in the whipping process;
Composite catalyst is used 10 parts alcohol in advance, and with water: alcohol=weight ratio was dissolved in 3: 7;
All the other 95%～98% (v/v) alcohol fully dissolve with chemical monomer (acrylic amide, vinylformic acid, vinyl acetate between to for plastic) and mix, and accomplish this work in advance in 8～12 hours;
System temperature after arriving 40-50 ℃ mixes catalyzer spirituous solution and chemical monomer spirituous solution, pours the reactor drum stirring reaction into;
After adding reaction monomers, remain under the same temperature condition and reacted 150-160 minute, added sheet alkali restir 30-40 minute;
Elevated temperature to 65 ℃ also continues to vacuumize, and the distillation of volatilizing fully of alcohol in the reactor drum is reclaimed;
Blowing finishes, and then the sieve with sieve underfill aperture 2.0-3.0mm sieves, pulverizes, mixes.Process step such as Fig. 1.
Confirming of temperature of reaction.Look through the documents and materials of all relevant graft starchs, temperature of reaction all is to be controlled in such scope.On the other hand, the too high alcohol of temperature of reaction is volatile, and the outward appearance of product also possibly turned to be yellow simultaneously.Reaction temperature is spent low, and reaction efficiency is low.Because the alcohol amount ratio is less, in the course of processing, states of matter is a solid phase, and heat exchange is slow, and the big ups and downs of temperature also should not be arranged during the course.
The selection in reaction times.Experiment below we did: 45 ℃ of fixation reaction temperature, the consumption of composite catalyst are 0.4g/900g starch.Under the same again mixing speed condition.In different reaction times sections, take a sample, measure the index of graft starch then---percentage of grafting (is the percentage of grafting that extraction solvent calculates acrylic amide with the N).Result such as Fig. 2.
The consumption of sheet alkali mainly is to consider the neutralization reaction system, regulates the pH value to neutrality.Churning time 30-40 minute, as long as stir, let sheet alkali disperse fully, in system to neutrality till.
Further, the catalyzer spirituous solution is mixed with the chemical monomer spirituous solution pour the reactor drum stirring reaction in, from reactor drum, extract negative pressure with the gap mode.
After adding propylene class mix monomer, along with the carrying out of reaction, stirring resistance can increase gradually.If it is excessive to stir resistance, just take out a vacuum, make the alcohol volatilization a part of, content liquid reduces in the system, and stirring resistance can be smaller.
Advantage of the present invention and beneficial effect:
From documents and materials, do not see to have both at home and abroad and produce graft starch in spirit solvent phase condition.Do not see yet and on the basis of acetate starch, produce the complex denaturation graft starch.This patent adopts the solvent phase of low alcohol to oil ratio to produce CMS, and alternative PVA uses and replaced effect preferably on spinning sizing agent is used, and recently finishes watching and all can enough meet the need of market from sexual valence.The size film property excellence of comparing with other modified starch, a large amount of PVA of replacement use in textile sizing, and market afterreaction on probation is good.Spirit solvent is produced not consume water resources mutually, no wastewater treatment.A small amount of alcohol that consumes reclaims through last distillation fully.The present invention has selected the box-type reactor drum for use, has broken through the cost misgivings on using.
Patent of the present invention adopts a small amount of spirit solvent to produce mutually at home first, has solved following two problems:
Without water resources, there is not discharge of wastewater to handle.
The ternary mix monomer is grafted on the starch polymer under the spirit solvent condition.Improved the size film property of starch slurry greatly, satisfied the starching demand of weaving producer, substituted PVA environmental protection starching high Zhi Dimian kind.
Description of drawings
Fig. 1 is the complex denaturation graft starch preparing method's that uses of a kind of spinning sizing agent of the present invention a main technique schema.
Fig. 2 is the percentage of grafting of graft starch under the differential responses time.
Embodiment
Below in conjunction with accompanying drawing further explain content of the present invention.
Embodiment 1
The complex denaturation graft starch that a kind of spinning sizing agent is used, its proportioning is:
Acetate starch 900Kg
95% (v/v) alcohol 100Kg
Acrylic amide 40Kg
Vinylformic acid 10Kg
Vinyl acetate between to for plastic 40Kg
Sheet alkali (sodium hydroxide) 5Kg
Composite catalyst 0.2Kg
The finished product: 996Kg ± 5%
The viscosity of said acetate starch requires:
L：4.0-8.0mPa.S
M：8.1-12.0mPa.S
H：12.1-16.0mPa.S
Substitution value: 0.10 ± 10%.
Said composite catalyst is composited by 1: 1 weight ratio by cerous sulfate and Potassium Persulphate.
The making method of the complex denaturation graft starch that a kind of spinning sizing agent is used, step is:
In the box reactor drum of band strong mixer, add the 900kg acetate starch, be heated to 45 ℃ in the whipping process;
Composite catalyst 0.2-0.5kg uses the alcohol of 10Kg in advance, and with water: alcohol=weight ratio was dissolved in 3: 7;
80kg 95% (V/V) alcohol and chemical monomer are that acrylic amide, vinylformic acid and vinyl acetate between to for plastic fully dissolve and mix, and accomplish this work in advance in 10 hours;
System temperature after arriving 40-50 ℃ mixes catalyzer spirituous solution and chemical monomer spirituous solution, pours the reactor drum stirring reaction into;
After adding reaction monomers, remain under the same temperature condition and reacted 150-160 minute, added 5kg sheet alkali restir 30-40 minute;
Elevated temperature to 65 ℃ also continues to vacuumize, and the distillation of volatilizing fully of alcohol in the reactor drum is reclaimed;
Blowing finishes, and then the sieve with sieve underfill aperture 2.0-3.0mm sieves, pulverizes, mixes.
The catalyzer spirituous solution is mixed with the chemical monomer spirituous solution pour the reactor drum stirring reaction in, from reactor drum, extract negative pressure with the gap mode.
The complex denaturation graft starch that adopts the inventive method to extract has following sign characteristics:
Outward appearance: white or yellow powder are granular
Fugitive constituent :≤14.0%
Viscosity: L:4.0-8.0mPa.S M:8.1-12.0mPa.S H:12.1-16.0mPa.S
(NDJ-79 type rotational viscosimeter is equal to reference to GB12098-89)
Viscosity stability:＞85.0% (weaving modified starch size quality industry standard commonly used, 2000 editions, tentative)
PH value: 6.0-7.0
Grafting index: A percentage of grafting＞10% (is the percentage of grafting that extraction solvent calculates acrylic amide with the N), B monomer reaction efficient＞99%.
Embodiment 2
The composite catalyst consumption is 0.52kg, alcohol (volumetric concentration 98%) consumption 80kg, and all the other are with embodiment 1.Effect is identical.
Embodiment 3
45 ℃ of fixation reaction temperature, the consumption of composite catalyst are the 0.4g/900g acetate starch, and all the other raw material amount ratios are with embodiment 1.Under the same again mixing speed condition.In different reaction times sections, take a sample, measure the index of graft starch then---percentage of grafting (is the percentage of grafting that extraction solvent calculates acrylic amide with the N), the result is as shown in Figure 2.
Percentage of grafting increases along with the prolongation in reaction times in initial reaction stage, and after reaction reached 150 minutes, this index did not almost change, and thinks that reaction is complete.So the time of selective reaction is 150-160min.
Claims (4)
1. the complex denaturation graft starch that spinning sizing agent is used is characterized in that, proportioning is the raw material of following weight part:
900 parts of acetate starchs
Volumetric concentration 95%～98% alcohol 80-100 part
40 parts of acrylic amides
10 parts in vinylformic acid
40 parts of vinyl acetate between to for plastics
5 parts in sheet alkali
Composite catalyst 0.2-0.5 part;
The viscosity of said acetate starch requires:
L:4.0-8.0mPa.S
M:8.1-12.0mPa.S
H:12.1-16.0mPa.S
Substitution value: 0.10 ± 10%.
2. the complex denaturation graft starch of using according to the said spinning sizing agent of claim 1 is characterized in that said composite catalyst is composited by cerous sulfate and Potassium Persulphate.
3. the making method of graft starch according to claim 1 is characterized in that, may further comprise the steps:
In the box reactor drum of band strong mixer, add acetate starch, be heated to 40-50 ℃ in the whipping process;
Composite catalyst water in advance and 10 parts of alcohol dissolvings, water and alcohol weight ratio 3:7;
70 parts of volumetric concentration 95%～98% alcohol and chemical monomer: acrylic amide, vinylformic acid and vinyl acetate between to for plastic fully dissolve and mix, and accomplish this work in advance in 8～12 hours;
System temperature after arriving 40-50 ℃ mixes catalyzer spirituous solution and chemical monomer spirituous solution, pours the reactor drum stirring reaction into;
After adding reaction monomers, remain under the same temperature condition and reacted 150-160 minute, added sheet alkali restir 30-40 minute;
Elevated temperature to 65 ℃ also continues to vacuumize, and the distillation of volatilizing fully of alcohol in the reactor drum is reclaimed;
Blowing finishes, and then the sieve with sieve underfill aperture 2.0-3.0mm sieves, pulverizes, mixes.
4. according to the making method of the said graft starch of claim 3, it is characterized in that the catalyzer spirituous solution is mixed with the chemical monomer spirituous solution pour the reactor drum stirring reaction in, from reactor drum, extract negative pressure with the gap mode.
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| CN103044624B (en) * | 2012-12-07 | 2015-10-21 | 宜兴市军达浆料科技有限公司 | A kind of High-film-forming-prhigh-performance high-performance cationic graft starch and preparation method thereof |
| CN103902840A (en) * | 2014-04-17 | 2014-07-02 | 西达（无锡）生物科技有限公司 | Method for improving performance of starch slurry film |
| CN107385911B (en) * | 2017-07-24 | 2020-03-24 | 西达（无锡）生物科技有限公司 | Adhesion promoter and preparation method and application thereof |
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| CN101376678B (en) * | 2008-10-10 | 2011-01-26 | 上海西达实业有限公司 | Formula of acetate starch and preparation technique thereof |
| CN101463563A (en) * | 2009-01-08 | 2009-06-24 | 四川大学 | Modified starch/polyacrylamide textile slurry composition and preparation thereof |
| CN101550658A (en) * | 2009-05-13 | 2009-10-07 | 四川省射洪聚塔化工有限公司 | Method of preparing improved plant starch textile sizing agent |
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